EP3318590A1 - Procédé de séparation de composés volatils provenant de produits visqueux à l aide d'un évaporateur en couche mince, et résine d'acide polylactique - Google Patents

Procédé de séparation de composés volatils provenant de produits visqueux à l aide d'un évaporateur en couche mince, et résine d'acide polylactique Download PDF

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Publication number
EP3318590A1
EP3318590A1 EP16197639.4A EP16197639A EP3318590A1 EP 3318590 A1 EP3318590 A1 EP 3318590A1 EP 16197639 A EP16197639 A EP 16197639A EP 3318590 A1 EP3318590 A1 EP 3318590A1
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EP
European Patent Office
Prior art keywords
thin
polymer melt
temperature
film
treatment chamber
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Granted
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EP16197639.4A
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German (de)
English (en)
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EP3318590B1 (fr
Inventor
Udo Mühlbauer
Rainer Hagen
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Uhde Inventa Fischer GmbH
ThyssenKrupp AG
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Uhde Inventa Fischer GmbH
ThyssenKrupp AG
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Application filed by Uhde Inventa Fischer GmbH, ThyssenKrupp AG filed Critical Uhde Inventa Fischer GmbH
Priority to EP16197639.4A priority Critical patent/EP3318590B1/fr
Priority to TW106135490A priority patent/TWI675691B/zh
Priority to US16/346,899 priority patent/US11447604B2/en
Priority to PCT/EP2017/078115 priority patent/WO2018086988A1/fr
Priority to CN201780068716.7A priority patent/CN109952334B/zh
Publication of EP3318590A1 publication Critical patent/EP3318590A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/88—Post-polymerisation treatment
    • C08G63/90—Purification; Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/0082—Regulation; Control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/06—Evaporators with vertical tubes
    • B01D1/065—Evaporators with vertical tubes by film evaporating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/785—Preparation processes characterised by the apparatus used

Definitions

  • the present invention relates to a process for the separation of compounds in the gaseous state of aggregation of PLA-containing products in a viscous state by means of a thin-film evaporator.
  • the compounds may be contained in the products under normal conditions in liquid or solid state.
  • the invention further relates to a polylactide resin prepared according to the process of the invention.
  • Polylactic acid is predominantly produced by ring-opening polymerization of lactide in the melt at final temperatures between 160 ° C and 200 ° C.
  • the polymerization leads to a chemical ring-chain equilibrium in which, depending on the final temperature between 3% and 5% of unreacted monomer.
  • the polymerization may be terminated even at incomplete conversion, the monomer concentration may then be up to 20% or more, depending on economic considerations. In any case, this must be unreacted Monomer can be separated from the polymer to produce a technically useful PLA.
  • a residual monomer content of ⁇ 0.5% is a condition to avoid smoldering, contamination and corrosion of the environment with lactide during processing from the melt.
  • larger residual monomer concentrations adversely affect the mechanical and thermal properties of PLA articles.
  • residual lactide in the PLA promotes hydrolytic degradation by absorbing atmospheric moisture.
  • the separation is done on an industrial scale usually by evaporation in vacuo (vacuum demonomerization).
  • vacuo vacuum demonomerization
  • the most diverse apparatuses including degassing extruders, extractors, disk reactors and thin film evaporators.
  • the latter are based on the principle that by distributing material in a thin layer on the inner surface of a temperature-controllable housing wall, a high heat flux density can be achieved, which ultimately a large evaporation performance and high evaporation ratios can be made possible in one run.
  • corresponding thin-film evaporators which are additionally equipped with a material promotion, are known in the art under the name Filmtruder.
  • a thin film processing device in the form of a film extruder is approximately in the CH 523 087 described, according to which in a heatable and / or coolable treatment chamber coaxial, a drivable rotor is arranged, which has a tubular body, on whose circumference inclined wings are evenly distributed and on the otherwise axially in the vicinity of the inner surface of the housing shell reaching or the inner surface touching Wiper blades are arranged.
  • the material to be treated is detected by the rotated wiper blades and distributed in a thin layer on the inner wall of the housing, while the inclined wing parts give the detected material a directed towards the outlet movement component.
  • the industrial scale requires an economic process in order to compete with existing, mostly crude oil-based polymers in price.
  • the economy of a process results from the investment costs for the apparatus and their installation and the operating costs resulting from the consumption of energy and auxiliary materials.
  • Multi-stage processes with numerous apparatuses are therefore to be avoided as well as the use of entrainers, which facilitate the evaporation of the monomer and thus lead to a lower residual monomer content, but at the same time increase the operating costs.
  • degassing extruder or thin film evaporator are proposed for monomer removal.
  • the vapors from the degassing are deposited in one or more cascaded capacitors.
  • entrainers such as nitrogen, toluene, ethylbenzene is mentioned as a possibility.
  • WO 98/36012 preferably for vacuum evaporation, a falling strand degasser, wherein the polymer melt falls in the form of threads in a container apparently not under vacuum down.
  • Hot inert gas such as nitrogen or dry air, is blown into the degasser to facilitate evaporation of the lactide from the surface of the falling filaments.
  • the lactid Vietnamese hot gas is cooled after leaving the degassing rapidly to 20-40 ° C, wherein lactide precipitates as crystalline dust. This is preferably done in a "crystallization chamber" by mixing with cold air.
  • EP 1 070 097 describes a process for the production of PLA starting from lactide, consisting of the following process steps: polymerization, stabilization, demonomerization, granulation and crystallization / drying.
  • demonomerization the apparatuses and machines also mentioned in the above-mentioned documents are mentioned.
  • Thin-film evaporation is the preferred method because of the good surface renewal by the rotors, which promotes vaporizing of the dilactide.
  • the font indicates the preferred pressure range between 0.5 mm Hg and 5 mm Hg and the temperature range between 200 ° C and 260 ° C. The ranges given are very wide and, especially for temperature, the upper limits are outside practicable values.
  • PLA is known to be temperature sensitive and should not be processed above 240 ° C, more preferably not over 220 ° C; see, for example, the "Processing Guides" of NatureWorks, the applicant's PLA-producing subsidiary, Cargill.
  • the specification is limited to a general description of the thin film evaporation and its application to the demonomerization of PLA in said pressure and temperature ranges.
  • process parameters such as rotor peripheral speed, viscosity of the PLA melt, residence time in the apparatus, monomer content and molecular weight before and after the demonomerization.
  • energy is introduced into the enamel by the rotor movement and thereby increases the temperature of the melt. It either does not seem to be known to the applicant, or it approves of it. On the latter leaves the large temperature range shut down. In this case, however, a marked reduction in molecular weight and thus thermal product damage, which often manifests itself in the form of yellowing, can be expected.
  • black bacon In addition, in a cone without forced delivery to the discharge pump dead zones in which the product persists for a long time and degrades to black, solid particles, often referred to in the art as black bacon. These black bacons are found in the product and cause problems when processed into films, bottles and fibers.
  • thin film processing devices are designed for the treatment of viscous material.
  • polylactide which is a temperature-sensitive material
  • the process heat should be kept as high as possible.
  • the process heat should be kept as high as possible in order to ensure the highest possible evaporation performance.
  • a high diffusion coefficient should be obtained by the high process heat in order to promote the mass transfer.
  • the thermal load and the residence time during demonomerization are low and the product does not suffer any damage which can be manifested in a significant reduction in molecular weight and product discoloration.
  • the removal of the monomer should be complete, which is understood to mean at least a 5-fold, better 10-fold reduction in the monomer content.
  • the residual monomer content of the product should preferably be below 0.5%.
  • the process must be economical for large-scale production plants, which means the lowest possible operating and investment costs. It is particularly important that the evaporated from the melt dilactide is recovered and used again in the ring-opening polymerization.
  • Claim 25 relates to a polylactide resin which can be produced in particular by the method according to the invention, which has special product properties.
  • the dependent claims are each advantageous developments.
  • the treatment chamber of the thin-film treatment apparatus thus corresponds to the interior of the housing in which the polymer melt containing polylactide and / or poly (co) lactide is subjected to the process according to the invention, in which, in particular, a separation of volatile components, in particular by distillation, degassing and / or drying, from the polymer melt becomes. It is designed generally cylindrical, but is conceivable or preferred that it is configured conically tapered in the outlet end portion.
  • a discharge pump preferably a gear pump, is arranged in the outlet-side end region of the housing for discharging the polymer melt from the thin-film treatment device.
  • viscous state of aggregation is typically understood as meaning a polymer melt having a viscosity in the range from 1 to 50,000 Pa.s, in particular from 50 to 15,000 Pa.s.
  • the material to be treated according to the invention has at least temporarily a viscosity of more than 100 Pa.s, more preferably more than 300 Pa.s, more preferably more than 500 Pa.s, most preferably 1000 Pa.s to 6000 Pa.s, since from this viscosity, the dissipation phenomena increase sharply and the advantages of the invention become particularly evident.
  • the determination of the viscosity may e.g. with a rotational viscometer according to DIN ISO 1652: 2013-02 at the respective temperature of the polymer melt.
  • the generated film of the polymer melt distributed on the inner surface of the treatment chamber can be locally monitored for its temperature.
  • the temperature readings obtained can be used, on the one hand, to set optimum temperature conditions of the product film, On the other hand help to prevent exceeding or falling below critical temperatures.
  • the invention thus makes it possible to locally determine the temperature of the film of the polymer melt and, owing to the determined temperature or the specific temperature profile, e.g. set at least one process parameter depending on a deviation from a setpoint.
  • the amount of heat to be introduced into the polymer melt can be controlled, e.g. by appropriate temperature control of the housing shell to adjust the process heat locally to the desired value, which in the case of a thin-film evaporation is typically high enough to ensure a high evaporation performance, and deep enough to a critical temperature, from which a thermal damage to the material to be treated must not be exceeded.
  • the housing jacket can be heated or cooled by means of a preheated heat transfer medium.
  • the setting of the process heat can also be regulated via the geometry and / or the rotational speed of the rotor shaft.
  • the present invention thus allows to ensure stable and reproducible operation and to enable the production of high quality products.
  • the compounds to be inhibited are selected from the group consisting of lactide, lactic acid, lactic acid dimers and, under the given process conditions, gaseous lactic acid oligomers, water and polymer synthesis additives, e.g. Catalysts, initiators or stabilizers and combinations thereof.
  • the rotor blades are operated at a rotational speed of 0.1 to 10 m / s, preferably 0.5 to 3 m / s, particularly preferably 0.5 to 2 m / s.
  • a shear rate of at most 1000 l / s, preferably 100 to 500 l / s, particularly preferably 200 to 300 l / s is set, the shear rate being the quotient of the rotational speed and distance of the rotor blades from the inner wall of the Treatment chamber is.
  • an element can be arranged on the rotor shaft in the outlet region, which promotes the polymer melt in the direction of the outlet nozzle during rotation of the rotor shaft.
  • This conveyor element may be formed, for example, as a screw conveyor or screw or a ring with a plurality of webs. A corresponding wreath is for example in the CH 523087 described.
  • the housing jacket is designed to be heatable and / or coolable.
  • a housing shell cavity is formed in the interior of the housing shell, which are intended to be traversed by a heat transfer medium for the purpose of heating and / or cooling.
  • the housing shell wall is configured double-walled and the space between the housing shell inner wall and Gesimousemantelauswand is intended to be traversed by the heat transfer medium.
  • the housing jacket comprises at least two housing jacket segments which are designed to be heated and / or cooled independently of one another.
  • each casing shell segment is preferably associated with a separate heat transfer medium circulation system with separate heat transfer inlet and separate heat transfer outlet.
  • the housing shell segments each enclose a corresponding treatment chamber zone and the temperature sensors are distributed to different treatment chamber zones.
  • the treatment chamber is thus subdivided into different treatment chamber zones in which a relatively large change in the composition or in the viscosity of the material is expected in comparison to the preceding treatment chamber zone.
  • Particularly preferred are in those treatment chamber zones in which due to the expected increase in viscosity and a relatively high entry of dissipation energy is expected, several temperature sensors arranged to monitor just in these treatment chamber zones the temperature in relatively high resolution and ultimately exceeding a critical Reliably avoid temperature. This is the case in particular in the outlet-side end region of the treatment chamber.
  • the temperature value of the polymer melt is used for adjusting the temperature of the heatable and / or coolable housing shell to a predetermined setpoint, in particular the housing shell at least two housing shell segments, each having at least one temperature sensor and a Separate adjustment of the temperature in each housing shell segments by means of a respective measured value of the temperature of the film of the polymer melt takes place in the respective housing shell segment.
  • a reduced pressure compared to normal conditions preferably a pressure of below 100 mbar, more preferably below 10 mbar, more preferably below 1 mbar.
  • the discharged compounds are preferably recovered in a downstream apparatus for the recovery of gaseous compounds, in particular from the gaseous state of aggregation by condensation and / or desublimation.
  • the residence time of the polymer melt in the thin-film treatment device is preferably from 2 to 4 minutes, preferably from 5 to 10 minutes.
  • the temperature of the heatable housing jacket, in particular in each of the housing jacket segments is set to a lower temperature than the temperature of the polymer melt introduced into the treatment chamber, in particular to a temperature of 130 to 250 ° C, preferably 160 to 240 ° C, in particular 180 to Tempered at 220 ° C.
  • the temperature of the polymer melt is determined for this purpose at the inlet port.
  • An inert gas is preferably introduced into the atmosphere in the interior of the thin-film treatment device (10), in particular via the rotor shaft (34), preferably nitrogen, dried air and / or argon.
  • the injection of inert gas can be carried out in particular instead of reducing the pressure to below 1 mbar, thereby facilitating the evaporation of the monomer by introducing an inert gas into the thin-film evaporator.
  • the presence of the inert gas acts as a pressure reduction in that it reduces the partial pressure of the monomer in the gas phase, which in turn increases the driving concentration difference between melt and gas phase. In this way, the demonomerization can e.g. Above the triple point pressure of lactide take place at the same time very good demonomerization. If you want to lower the residual monomer content even further, the inert gas can also be added at a pressure in the thin-film evaporator of less than 1 mbar.
  • the inlet of the thin-film treatment device is preferably preceded by a mixing device, preferably a static mixer. Over this entry of the polymer melt in the treatment chamber deactivators, additives, stabilizers or mixtures and combinations thereof can be applied in the polymer melt.
  • the invention relates to a process for demonomerizing a PLA melt in a thin film evaporator. It is particularly applicable to any polymer melt consisting essentially of lactide structural units, independently of the enantiomeric composition, and prepared in a ring-opening polymerization.
  • the temperature of the products to be demonomerized can be locally resolved and continuously monitored.
  • the measured values obtained can be used for the controlled setting of the temperatures in the heatable or coolable jacket of the thin-film treatment apparatus, in particular of the thin-film evaporator, as a manipulated variable. So z. B. occurring in the product unpredictable temperature rises are detected early and compensated. This allows the demonomerization of a particular product in the optimum temperature range, so that on the one hand as high as possible Demonomerization achieved, on the other hand, thermal damage to the product can be prevented.
  • the content of the compounds in the product after passing through the thin film treatment device, in particular the thin film evaporator can be significantly reduced, in particular reductions to a maximum of 0.2 times, preferably not more than 0.1 times the content of the compounds before passing through the thin film treatment device, in particular Thin-film evaporator achievable.
  • a residual monomer content in the product of less than 0.5% can be achieved.
  • the method according to the invention makes it possible that the yellow discoloration, measured as b * value, during the performance of the method is increased by not more than 4 scale values and the b * value in the product is less than 15.
  • the special process control allows no dead zones to form in the thin-film evaporator.
  • the formation of so-called "black bacon” can be largely prevented.
  • a maximum of 50 black bacon per kilogram discharged product when carrying out the process according to the invention, a maximum of 50 black bacon per kilogram discharged product. The product thus contains less than 50 black bacons per kilogram.
  • Preferred pressures which can be applied to the thin-film evaporator, for example via the at least one vapor outlet, are advantageously below 100 mbar, more preferably below 10 mbar, particularly preferably below 1 mbar. This reliably makes it possible for volatile compounds contained in the product to change into the gaseous state of aggregation and thereby out of the interior space via the at least one Brüdenstutzen be discharged and the discharged compounds are preferably recovered in the apparatus for recovering gaseous compounds in particular from the gaseous state of aggregation by condensation and / or desublimation.
  • the demonomerization is thus operated in particular in a vacuum. The lower the vacuum, the better the demonomerization performance.
  • the thin film processing apparatus preferably the thin film evaporator, is operated at a pressure of less than 10 mbar (absolute).
  • the invention additionally relates to a polylactide resin which can be prepared in particular according to the method described above.
  • a polylactide resin which can be prepared in particular according to the method described above.
  • the thin-film treatment apparatus preferably the thin-film evaporator polylactide introduced in the viscous aggregate state via the inlet nozzle in the thin film evaporator, within the thin-film evaporator, a film of polylactide is produced, while at least part of the monomers in the product, in this case lactide, in the gaseous Transferred state of aggregation and discharged lactide with the gas phase from the thin-film evaporator.
  • the product according to the invention is characterized by a weight average molecular weight of between 50,000 g / mol and 500,000 g / mol, a yellow color measured as b * value of less than 15, a residual monomer content of less than 0.5 wt .-% and less than 50 BS / kg off.
  • Lactide is the cyclic diester of lactic acid. Lactide is understood as meaning both the L, L-dilactide and also the D, D-dilactide as well as the meso-dialctide consisting of an L and a D unit.
  • Demonomerization Separator or apparatus for separating monomer from a polymer by converting the monomer into the gas phase and separating the monomer-containing gas phase from the polymer.
  • other volatile components are always present in the polymer, such as lactic acid, cyclic and linear oligomers, and thermal polymer degradation products, which are separated together with the monomer. Because of their low concentration compared to the monomer they are not mentioned in the text and are always included in the term "monomer”.
  • Thin Film Evaporator A vertical, cylindrical apparatus with an internal wiper system which distributes the incoming polymer melt uniformly to the externally temperable surface and conveys it downwards. Due to the conveying effect of the rotor blades, a constantly renewing melt surface is generated. The residence time in the apparatus and the surface renewal rate can be adjusted by varying the speed of rotation of the rotor. The discharge of the melt from the apparatus is supported by the specially shaped in the discharge cone rotor shaft.
  • Tempering zone Area of the thin film evaporator in which the temperature can be adjusted by a heat transfer medium, which flows in the shell of the thin film evaporator in this zone.
  • a thin film evaporator can have up to five independent tempering zones.
  • Triple Point Point in the pressure-temperature diagram of a substance in which all three phases, solid, liquid and vapor, coexist. At the triple point the phase boundary lines meet solid / liquid, liquid / vapor and solid / vapor.
  • Desublimation Direct transfer of a substance from the vapor state to the solid state at pressures and temperatures below the triple point, ie without passing through the liquid state. The reversal of sublimation.
  • Stabilization In order to prevent the monomer from regressing after polymerization and demonomerization and thus deteriorate the product quality, the catalyst for ring-opening polymerization must be deactivated by addition of suitable additives. Suitable substances for stabilization are described in the relevant literature.
  • Black specks Small solid particles, mostly carbon-based, that are formed by degradation of the polymer due to long residence times at high temperatures and have an (averaged) diameter greater than 100 microns so that they are visible to the naked eye in the product , If an apparatus for processing polymers produces black bacon, this is an indication of dead zones within the apparatus, ie areas which are not flown through and in which polymer can deposit and degrade. The degraded polymer is then washed from time to time as Black Bacon with the polymer from the apparatus.
  • the invention relates to a process for demonomerizing a PLA melt in a thin film evaporator. It is applicable to any polymer melt consisting essentially of lactide structural units, independent of the enantiomeric composition, prepared in a ring-opening polymerization.
  • FIG. 1 shows an embodiment of a thin film treatment device according to the invention in the form of a thin film evaporator 1, as used in the inventive method.
  • a thin-film evaporator 1 for example, monomer-containing PLA, in particular directly after the continuous polymerization as liquid or viscous melt can be continuously introduced into the thin-film evaporator 1 via an inlet connection 2.
  • the molten viscous PLA is uniformly distributed in the treatment chamber 13 of the thin film evaporator 1 of wiper blades 3, which are connected to a central rotor shaft 6 on the temperature-controllable inner surface of the treatment chamber 13 and thereby transported down.
  • the apparatus is further distinguished by the fact that the central rotor shaft 6 in the conical outlet region is equipped with specially shaped conveying elements 4, for example a conveying screw, which press the viscous melt into the intake region of the discharge pump 5.
  • the discharge pump 5 is a gear pump with a specially shaped, very wide catchment area.
  • the wiper blades 3 and the discharge screw 4 are designed so that a residence time of the melt of 20 min is not exceeded in the entire thin film evaporator and no dead zones, which lead to the degradation of the product arise.
  • the evaporated from the melt monomer is withdrawn via the vapor nozzle 7 in countercurrent to the melt flow from the thin-film evaporator 1.
  • the temperature of the apparatus is done by a heat transfer medium, which is circulated in the jacket 10 of the thin film evaporator 1 by means of a pump 12 and whose temperature can be adjusted.
  • the thin-film evaporator 1 has at least one housing jacket segment 10.
  • the temperature of the heat-transfer medium must both be actively increased by a heater 8 and actively cooled by a cooler 9.
  • the heater 8 is needed especially for the starting process, so that the thin-film evaporator 1 can be heated to process temperature (180 ° C - 220 ° C).
  • the cooling 9 is an essential element for the operation. It ensures that the product temperature does not increase too much during demonomerization and that the product is not damaged.
  • the thin-film evaporator 1 has three temperature sensors 11.
  • the temperature sensors 11 dip into the film of the product. Thus, at different points of the product mixture constantly monitoring the temperature.
  • inert gas can be added to the treatment chamber 13 via the central rotor shaft 6 in order to improve the removal of de-ionization power.
  • the demonomerization is operated in a vacuum.
  • the thin film evaporator is operated at a pressure of less than 10 mbar (absolute).
  • FIG. 2 Another embodiment of a thin-film treatment device according to the invention is shown in FIG FIG. 2 shown.
  • the thin-film evaporator 1 is substantially identical to FIG. 1 , as the sole and essential difference is to be mentioned that the cooling or tempering jacket comprises three separately heatable housing shell segments 10a, 10b and 10c. These individual housing shell segments 10a, 10b and 10c are each supplied via a separate circuit A, B and C for temperature control of the respective housing shell segments 10a, 10b and 10c of the heating or cooling jacket 10 of the thin-film evaporator 1.
  • different temperature ranges can be selected at different vertical locations of the thin film evaporator 1 or targeted temperature gradients can be set over the entire thin film evaporator 1.
  • Each cooling or heating circuit A, B and C for the individual housing shell segments 10a, 10b and 10c of the tempered jacket 10 of the thin film evaporator 1 has a separate pump 12 and heating elements 8 and cooling elements 9.
  • the housing shell segments 10b and 10c have this Temperature sensors 11; For example, two temperature sensors are accommodated in the housing jacket segment 10b, and another temperature sensor 11 is accommodated in the housing jacket segment 10c.
  • the housing jacket segments 10a discharge zone
  • the housing shell segment 10c undergoes a further subdivision, it may be provided, for example, to temper the part separately below the inlet nozzle 2, while the part above the inlet nozzle 2, in which the vapor nozzle 7 is located, also via a separate Temperier Vietnamese features. In this case, it may then be provided that no temperature sensor is present in the upper casing shell segment (tempering zone), whereas, in the separate casing shell segment formed below the inlet nozzle 2, a temperature sensor 11 is present.
  • FIG. 3 shows an embodiment of the thin-film evaporator according to the invention to which a static mixer C is connected upstream and a device for condensation E of the discharged gaseous compounds is connected downstream.
  • the thin-film evaporator comprises two temperature sensors 11.
  • the static mixer C is connected to the inlet for product (see reference 2 in FIG. 1 ), while the condensation device E is connected to the vapor tube (see reference numeral 7 in FIG FIG. 1 ) of the thin-film evaporator.
  • the thin-film evaporator according to FIG. 3 includes two temperature sensors 11 and 11 ', which are formed according to the embodiments of the thin film evaporator according to the figures described above.
  • the evaporation of the monomer can be facilitated by introducing an inert gas into the thin-film evaporator.
  • the presence of the inert gas acts as a pressure reduction in that it reduces the partial pressure of the monomer in the gas phase, which in turn increases the driving concentration difference between melt and gas phase. In this way, the demonomerization can take place above the triple point pressure of dilactide with simultaneously very good demonomerization performance. If you want to lower the residual monomer content even further, the inert gas can also be added at a pressure in the thin-film evaporator of less than 1 mbar.
  • the PLA sample is dissolved in chloroform and precipitated with isopropanol.
  • the precipitated PLA is filtered off, while the low molecular weight components remain in the solution.
  • pentamethylbenzene as an internal standard, the solution in the gas chromatograph on a capillary column DB-5; 15 / 0.32 separated into their components and quantitatively detected lactide with a flame ionization detector.
  • the color values are determined on powder-ground, amorphous polymer.
  • the polymer may be present either as strands (before demonomerization) or as amorphous granules (after demonomerization).
  • the color values of the L * a * b * color space are measured using a color spectrophotometer calibrated against a white standard. The light from a standard light source is reflected by the powdered polymer. The intensity of the reflected radiation is determined by a photocell. The L * value indicates the brightness.
  • the color of the sample material is described by two axes, where the b * values indicate the discoloration towards blue (negative b * value) or yellow (positive b * value).
  • the a * value indicates the red or green tint.
  • Example 1 Demonomerization of a low molecular weight PLA melt in a thin-film evaporator according to the invention
  • a stabilizer for deactivating the catalyst is mixed in a static mixer.
  • the molecular weight of the polymer after the tube reactor is 171,000 g / mol and the monomer content 4.8%.
  • the b * color value was determined to be 5.4.
  • the temperature at the entrance is 186 ° C.
  • the melt enters a thin-film evaporator equipped with 4 tempering zones. Two temperature measuring points '11 are attached to the stirrer shaft, which can measure the temperature of the melt in the thin-film evaporator directly.
  • the temperature sensor 11 is arranged at the level of the second tempered zone, which connects to the entry zone (with inlet for the product) below.
  • the second temperature sensor 11 ' is arranged at the level of the third tempered zone (below the second zone). Entry and discharge zones do not have temperature sensors.
  • the flow temperatures of the heat transfer media were set to 192 ° C in all 4 temperature control zones. In the stationary state, a product temperature of 203 ° C. was established at the upper temperature measuring point 11, and a product temperature of 205 ° C. at the lower temperature measuring point 11. After demonomerization, a monomer content of 0.16% was measured. The molecular weight was 168,000 g / mol and the b * color value was unchanged. The numerical values are summarized in the table below.
  • Example 2 Demonomerization of a high molecular weight PLA melt in a thin-film evaporator according to the invention
  • Example 3 Demonomerization of a high molecular weight PLA melt in a thin film evaporator according to the invention without cooling
  • Example 2 The procedure of Example 2 was repeated, except that no stabilizer was metered before the demonomerization. As can be seen from the data in the table, the monomer content after thin film evaporation increases above 1.5%. The monomer content is thus reduced only by a factor of 2.7. The stabilization of the PLA melt must therefore be done before the demonomerization.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
EP16197639.4A 2016-11-08 2016-11-08 Procédé de séparation de composés volatils provenant de produits visqueux à l aide d'un évaporateur en couche mince Active EP3318590B1 (fr)

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EP16197639.4A EP3318590B1 (fr) 2016-11-08 2016-11-08 Procédé de séparation de composés volatils provenant de produits visqueux à l aide d'un évaporateur en couche mince
TW106135490A TWI675691B (zh) 2016-11-08 2017-10-17 用於以薄膜蒸發器自黏性產品移除揮發性化合物之方法及聚乳酸樹脂
US16/346,899 US11447604B2 (en) 2016-11-08 2017-11-03 Method for the separation of volatile compounds from viscous products by means of a thin-film evaporator, and polylactide resin
PCT/EP2017/078115 WO2018086988A1 (fr) 2016-11-08 2017-11-03 Procédé pour séparer des composés volatils à partir de produits visqueux avec un évaporateur à couche mince et résine polylactide
CN201780068716.7A CN109952334B (zh) 2016-11-08 2017-11-03 用于通过薄膜蒸发器从粘性产物去除挥发性化合物的方法和聚丙交酯树脂

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CN110841318A (zh) * 2019-12-16 2020-02-28 江苏怡达化学股份有限公司 一种醇醚残液的固化分离方法及其分离***
EP4149989A1 (fr) * 2020-05-11 2023-03-22 Ethicon, Inc Développement de procédés de production de copolymère glycolide-l-lactide continue
CN112284573B (zh) * 2020-09-30 2022-01-14 深圳信息职业技术学院 一种具有散热功能的压力传感器

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CN109952334A (zh) 2019-06-28
EP3318590B1 (fr) 2020-08-05
WO2018086988A1 (fr) 2018-05-17
TW201821141A (zh) 2018-06-16
US11447604B2 (en) 2022-09-20
US20190352457A1 (en) 2019-11-21
TWI675691B (zh) 2019-11-01

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